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Structural versatility of the quasi-aromatic Mobius type zinc(ii)-pseudohalide complexes - experimental and theoretical investigations.

ABSTRACT: In this contribution we report for the first time fabrication, isolation, structural and theoretical characterization of the quasi-aromatic Möbius complexes [Zn(NCS)₂L^I] (1), [Zn₂(μ_1,1-N₃)₂(L^I)₂][ZnCl₃(MeOH)]₂·6MeOH (2) and [Zn(NCS)L^II]₂[Zn(NCS)₄]·MeOH (3), constructed from 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (L^I) or benzilbis(acetylpyridin-2-yl)methylidenehydrazone (L^II), respectively, and ZnCl₂ mixed with NH₄NCS or NaN₃. Structures 1-3 are dictated by both the bulkiness of the organic ligand and the nature of the inorganic counter ion. As evidenced from single crystal X-ray diffraction data species 1 has a neutral discrete heteroleptic mononuclear structure, whereas, complexes 2 and 3 exhibit a salt-like structure. Each structure contains a Zn^II atom chelated by one tetradentate twisted ligand L^I creating the unusual Möbius type topology. Theoretical investigations based on the EDDB method allowed us to determine that it constitutes the quasi-aromatic Möbius motif where a metal only induces the π-delocalization solely within the ligand part: 2.44|e| in 3, 3.14|e| in 2 and 3.44|e| in 1. It is found, that the degree of quasi-aromatic π-delocalization in the case of zinc species is significantly weaker (by ∼50%) than the corresponding estimations for cadmium systems - it is associated with the Zn-N bonds being more polar than the related Cd-N connections. The ETS-NOCV showed, that the monomers in 1 are bonded primarily through London dispersion forces, whereas long-range electrostatic stabilization is crucial in 2 and 3. A number of non-covalent interactions are additionally identified in the lattices of 1-3.

SUBMITTER: Mitoraj MP

PROVIDER: S-EPMC9069493 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Structural versatility of the quasi-aromatic Möbius type zinc(ii)-pseudohalide complexes - experimental and theoretical investigations.

Mitoraj Mariusz P MP Afkhami Farhad Akbari FA Mahmoudi Ghodrat G Khandar Ali Akbar AA Gurbanov Atash V AV Zubkov Fedor I FI Waterman Rory R Babashkina Maria G MG Szczepanik Dariusz W DW Jena Himanshu S HS Safin Damir A DA

RSC advances 20190731 41

In this contribution we report for the first time fabrication, isolation, structural and theoretical characterization of the quasi-aromatic Möbius complexes [Zn(NCS)2LI] (1), [Zn2(μ1,1-N3)2(LI)2][ZnCl3(MeOH)]2·6MeOH (2) and [Zn(NCS)LII]2[Zn(NCS)4]·MeOH (3), constructed from 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (LI</sup ...[more]

PMID: 35530624

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Project description:In this work, we report solvent-induced complexation properties of a new N2S2 tetradentate bis-thiosemicarbazone ligand (H2LI), prepared by the condensation of 4-phenylthiosemicarbazide with bis-aldehyde, namely 2,2'-(ethane-1,2-diylbis(oxy)dibenzaldehyde, towards nickel(II). Using ethanol as a reaction medium allowed the isolation of a discrete mononuclear homoleptic complex [NiLI] (1), for which its crystal structure contains three independent molecules, namely 1-I, 1-II, and 1-III, in the asymmetric unit. The doubly deprotonated ligand LI in the structure of 1 is coordinated in a cis-manner through the azomethine nitrogen atoms and the thiocarbonyl sulfur atoms. The coordination geometry around metal centers in all the three crystallographically independent molecules of 1 is best described as the seesaw structure. Interestingly, using methanol as a reaction medium in the same synthesis allowed for the isolation of a discrete mononuclear homoleptic complex [Ni(LII)2] (2), where LII is a monodeprotonated ligand 2-(2-(2-(2-(dimethoxymethyl)phenoxy)ethoxy)benzylidene)-N-phenylhydrazine-1-carbothioamide (HLII). The ligand LII was formed in situ from the reaction of LI with methanol upon coordination to the metal center under synthetic conditions. In the structure of 2, two ligands LII are coordinated in a trans-manner through the azomethine nitrogen atom and the thiocarbonyl sulfur atom, also yielding a seesaw coordination geometry around the metal center. The charge and energy decomposition scheme ETS-NOCV allows for the conclusion that both structures are stabilized by a bunch of London dispersion-driven intermolecular interactions, including predominantly N-H∙∙∙S and N-H∙∙∙O hydrogen bonds in 1 and 2, respectively; they are further augmented by less typical C-H∙∙∙X (where X = S, N, O, π), CH∙∙∙HC, π∙∙∙π stacking and the most striking, attractive long-range intermolecular C-H∙∙∙Ni preagostic interactions. The latter are found to be determined by both stabilizing Coulomb forces and an exchange-correlation contribution as revealed by the IQA energy decomposition scheme. Interestingly, the analogous long-range C-H∙∙∙S interactions are characterized by a repulsive Coulomb contribution and the prevailing attractive exchange-correlation constituent. The electron density of the delocalized bonds (EDDB) method shows that the nickel(II) atom shares only ~0.8|e| due to the σ-conjugation with the adjacent in-plane atoms, demonstrating a very weak σ-metalloaromatic character.

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Structural versatility of the quasi-aromatic Mobius type zinc(ii)-pseudohalide complexes - experimental and theoretical investigations.

Publications

Structural versatility of the quasi-aromatic Möbius type zinc(ii)-pseudohalide complexes - experimental and theoretical investigations.

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